145107-53-5Relevant academic research and scientific papers
Biocatalytic access to nonracemic γ-oxo esters: Via stereoselective reduction using ene-reductases
Turrini, Nikolaus G.,Cioc, Rǎzvan C.,Van Der Niet, Daan J. H.,Ruijter, Eelco,Orru, Romano V. A.,Hall, Mélanie,Faber, Kurt
, p. 511 - 518 (2017/08/14)
The asymmetric bioreduction of α,β-unsaturated γ-keto esters using ene-reductases from the Old Yellow Enzyme family proceeds with excellent stereoselectivity and high conversion levels, covering a broad range of acyclic and cyclic derivatives. Various strategies were employed to provide access to both enantiomers, which are versatile precursors of bioactive molecules. The regioselectivity of hydride addition on di-activated alkenes was elucidated by isotopic labeling experiments and showed strong preference for the keto moiety as activating/binding group as opposed to the ester. Finally, chemoenzymatic synthesis of (R)-2-(2-oxocyclohexyl)acetic acid was achieved in high ee on a preparative scale combining enzymatic reduction followed by ester hydrogenolysis.
Reduction of alkyl (2-oxocyclohexyl)acetates by baker's yeast.
Ganaha,Funabiki,Motoki,Yamauchi,Kinoshita
, p. 181 - 184 (2007/10/03)
Baker's yeast reduction of methyl and ethyl (2-oxocyclohexyl) acetates proceeded with enantio- and diastereo-selectivity, affording the corresponding (2S)-trans-alcohols (major), (2S)-cis-alcohols (minor), and the unaltered (1S)-ketones with high optical purity.
Stereoselectivity in hydrosilylative reduction of substituted cyclohexanone derivatives with chiral rhodium-bis(oxazolinyl)pyridine catalyst
Nishiyama,Park,Itoh
, p. 1029 - 1034 (2007/10/02)
Stereoselectivity in the reduction of substituted cyclohexanones, 4-tert-butylcyclohexanone, 2-methylcyclohexanone, 2-phenylcyclohexanone, and 2-methoxycarbonyl-methylcyclohexanone, was examined with chiral rhodium-bis(oxazolinyl)pyridine catalyst and diphenylsilane. 4-tert-Butylcyclohexanone gave the corresponding trans(equatorial)-alcohol predominantly; the ratio of the trans/cis alcohols, 67:33. Other 2-substituted cyclohexanones showed exclusive enantioselectivities for each diastereomer in terms of the kinetic resolution; e.g. from 2-phenylcyclohexanone, 99% ee of (1S,2R)-trans-2-phenylcyclohexanol and 96% ee of (1S,2S)-cis-2-phenylcyclohexanol in 92% yield (the trans/cis ratio = 51:49).
THE ASSYMETRIC MICHAEL REACTION OF (2R,3S)-3,4-DIMETHYL-2-PHENYLPERHYDRO-1,4-OXAZEPINE-5,7-DIONE WITH 1-NITROCYCLOHEXENE
Takeda, Takeshi,Hoshihiko, Tomonori,Mukaiyama, Teruaki
, p. 797 - 800 (2007/10/02)
Optically active (2-nitrocyclohexyl)acetic acid(III) was obtained by the Michael reaction of (2R,3S)-3,4-dimethyl-2-phenylperhydro-1,4-oxazepine-5,7-dione(I) with 1-nitrocyclohexene in the presence of potassium t-butoxide (or cesium fluoride) and crown et
Ouverture de dichlorocyclopropanes en presence d'un nucleophile interne. Absence de participation intramoleculaire. Rearrangement concerte en chlorures allyliques
Chiche, Laurent,Christol, Henri,Coste, Jacques,Pietrasanta, Francine,Plenat, Francoise
, p. 164 - 174 (2007/10/02)
It is shown that a conveniently placed internal nucleophile (carboxyl group) is not involved with the rearrangement of a diclorocyclopropane into an allylic chloride.This result appears to support a concerted mechanism of a ?s2 + ?a2 type for this rearrangement.In the products obtained, the allylic chloride may undergo displacement either by solvent (H2O), leading to alcohols, or by the internal carboxyl group, leading to a lactone.
